Nitro substituted azaalkanols and their method of preparation



United States Patent O NITRO SUBSTITUTED AZAALKANOLS AND THEIR METHOD OF PREPARATION Milton B. Frankel and Gustave B. Linden, Pasadena, Calif assignors to Aerojet-General I'orporation, Azusa, Calif., a corporation of Ohio No Drawing. Filed Dec. 19, 1957, Ser. No. 711,768

"16 Claims. (Cl. 260-584) This invention relates to new compositions of matter and to a method for their preparation. More particularly, the invention relates to azaalkanols of the following general formula:

wherein. R is a hydrogen, nitro, halogen, alkyl, nitroalkyl or halonitroalkyl radical; R is a hydrogen, halogen alkyl, nitroalkyl or halom'troalkyl radical; and A is an alkylene radical.

The azaalkanols of this invention react with nitric acid according to the method disclosed in our copending US. patent application, Serial No. 704,227, now Patent No. 2,934,558, issued April 26, 1960, filed concurrently with the present application, to form high energy nitrazaalkyl nitrates such as 3-aza-3,5,5-trinitro-l-hexylnitrate which are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent 2,470,162, issued May 17, 1949. One way of using thenitrazaalkylnitrates which can be prepared from the azaalkanols of the present invention in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufiiciently insensitive to withstand the shock entailed in the ejection'of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The novel azaalkanols of this invention are prepared by condensing a nitroalkanol with an alkanolamine in accordance with the general reaction scheme set forth below:

31 g. (0.5) glacial acetic acid (as a buffer), and 75 g. (90%, 0.45 mole) 2,2-dinitropropanol. After refluxing for 3 hours, most of the methanol was removed at reduced pressure, and the brown oil remaining was diluted with water. The diluted mixture was extracted twice with methylene chloride. The methylene chloride solution was washed once with a little water, twice with saturated sodium chloride solution, and dried over anhydrous calcium sulfate. The dried 3-aza-5,5-dinitro-1- hexanol product weighed 46 g and was in the form of a brown oil.

Reaction temperature is not critical in the practice of this invention, the only significant efliect of reaction temperature [variation being a corresponding increase or decrease in the rate of reaction. For purposes of convenience the condensation reaction of this invention can be carried out in a polar solvent in which the reactants are soluble, and when such a solvent is used the reaction is preferably accomplished by refluxing the resulting solution at its normal reflux temperature. Examples of suitable solvents for this purpose are alcohols such as methanol, ethanol, etc.; glycols such as ethylene glycol;

tetra-hydrofuran; dioxan; and any other polar organic solvents.

The nitroalkanol reactant of this invention is prepared by condensing a labile hydrogen containing nitroalkane such as geminaldinitroethane, with formaldehyde. This reaction is increasingly reversible with increasing basicity of the system and therefore, for optimum yields, it is desirable to conduct the condensation reaction of the present invention in the presence of a buffer, such as acetic acid, to reduce the tendency of the nitroalkanol to decompose into formaldehyde and the corresponding nitroalkane.

It will be appreciated that a wide variety of novel compounds within the scope of the present invention can be prepared in accordance with the method taught herein. For example, 2-nitro-l-propanol, 2-chloro-2,4-dinitro-1- butanol and 4-bromo-2,4-dinitro-l-pentanol condense with n-hexanolamine to yield 7-aza-9-nitro-l-decanol, 7- aza-9-chloro-9,ll-dinitro-l-undecanol and 7-aza-1lbromo-9,1l-dinitro-l-dodecanol, respectively. Other nitra za alkanols within the scope of our invention'can be prepared by condensing appropriate starting materials as taught herein.

We claim:

1. As new compositions of matter, azaalkanols having the general formula:

l. a wherein R is a radical selected from the group consisting of hydrogen, nitro, halogen, lower alkyl, lower nitroalkyl and lower halonitroalkyl radicals; R is a radical selected from the group consisting of hydrogen, halogen, lower alkyl, lower nitroalkyl and lower halonitroalkyl radicals; and A is a lower alkylene radical provided that when R is hydrogen R is a radical selected from the group consisting of hydrogen, halogen, lower nitroalkyl and lower halonitroalkyl radicals; when R is hydrogen R is a radical selected from the group consisting of hydrogen, halogen, lower nitroalkyl and lower halonitroalkyl radicals and when R is a nitro radical R is a radical selected from the group consisting of halogen, lower nitroalkyl and lower halonitroalkyl radicals.

2. As new compositions of matter, azaalkanols having the general formula:

i 1 RGCHzN--CH2AOH R wherein R is a halogen radical, R is a lower nitroalkyl radical and A is a lower alkylene radical.

3 3. As new compositions of matter, azaalkanols having the general formula:

wherein R is a halonitroalkyl radical and A is an alkylene radical.

4. As a new composition of matter, 7-aza-9-chloro- 9,1l-dinitro-l-undecanol, having the structural formula:

5. As a new composition of matter, 7-aza-11-bromo- 9,11-dinitro-1-dodecanol, having the structural formula:

6. The method of preparing azaalkanols having the general formula:

Rr-C-CHz-N-CHzA-OH comprising condensing a nitroalkanol having the general formula:

N 02 R(ilCH:r-OH

with an alkanolamine having the general formula:

NH CH AH wherein R is a radical selected from the group consisting of hydrogen, nitro, halogen, lower alkyl, lower nitroalkyl and lower halonitroalkyl radicals; R is a radical selected from the group consisting of hydrogen, halogen, lower alkyl, lower nitroalkyl and lower halonitroalkyl radicals; and A is a lower alkylene radical.

7. The method of preparing azaalkanols having the general formula:

comprising condensing a nitroalkanol having the general formula:

l IIO2 a-oonron with an alkanolamine having the general formula:

NH CH AOH wherein R is a nitro radical, R is a lower alkyl radical and A is a lower alkylene radical.

8. The method of preparing azaalkanols having the general formula:

N02 1; R+-CH2NCH2AOH 4 comprising condensing a nitroalkanol having the general formula:

ll Oa RC-CHn-OH with an alkanolamine having the general formula:

NH CH A-OH wherein R is a halogen radical, R is a lower nitroalkyl radical and A is a lower alkylene radical.

9. The method of preparing azaalkanols having the general formula:

comprising condensing a nitroalkanol having the general formula:

H-C-CH -OH R with an alkanolamine having the general formula:

NH CH A-OH wherein R is a lower alkyl radical and A is a lower alkylene radical.

10. The method of preparing azaalkanols having the general formula:

N02 1?: HCHzNCHzA-OH comprising condensing a nitroalkanol having the general formula:

with an alkanolamine having the general formula:

NI-I CH A-OH wherein R is a lower halonitroalkyl radical and A is a lower alltylene radical.

11. The method of preparing 3-aZa-5,5-dinitro-1- hexanol comprising condensing ethanolamine with 2,2- dinitropropanol.

12. The method of preparing 7-aza-9-nitro-1-decanol comprising condensing 2-nitro-1-pr0panol with n-hexanolamine.

13. The method of preparing 7-aza-9-chloro-9,1l-dinitro-1-undecanol comprising condensing 2chloro-2,4- dinitro-l-butanol with n-hexanolamine.

14. The method of preparing 7-aza-11-bromo-9,11- dinitro-l-dodecanol comprising condensing 4-bromo-2,4- dinitro-l-pentanol with n-hexanolamine.

15. The method of claim 6 wherein the condensation is carried out in a polar organic solvent.

16. The method of claim 11 wherein the condensation is carried out in methanol at reflux temperature.

References Cited in the file of this patent UNITED STATES PATENTS Bahner Oct. 24, 1950 Schenck et al Jan. 17, 1956 OTHER REFERENCES 

1. AS NEW COMPOSITIONS OF MATTER, AZAALKANOLS HAVING THE GENERAL FORMULA: 